Crystal structure of (E)-N-{2-[2-(2-chloro­benzyl­idene)hydrazin-1-yl]-2-oxoeth­yl}-4-methyl­benzamide monohydrate

The title compound is twisted in such a way that the almost planar [C_ar—C(=O)—N(H)—C(H₂] and [C(H₂)—C(=O)N(H)—N=C(H)—C_ar] segments are inclined to on another by 77.36 (8)°, while the benzene rings are inclined to one another by 89.69 (9)°. In the crystal, mol­ecules are linked via pairs of N—H...O hydrogen bonds, forming inversion dimers which are linked by O—H...O hydrogen bonds, involving the crystal water mol­ecule, forming chains propagating along the a-axis direction.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.103
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.021 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         18 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          7 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          4 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         20 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Chemical context

N-Acyl­hydrazones have been reported to be promising in terms of their future potential as anti­bacterial drugs (Osorio et al., 2012). These predictions have provided a therapeutic pathway to develop new effective biologically active Schiff-base derivatives. N-Acyl­hydrazones may exist as Z/E geometrical isomers about the C═N double bond and as syn/anti amide conformers (Palla et al., 1986). The carbonyl group in the acyl­hydrazone provides the possibility for electron delocalization within the hydrazone moiety. The anti-TNF-α activity of glycinyl-hydrazone derivatives indicate that differences in the hydro­phobicity of the imine-attached framework plays an important role. The study of conformational isomers of the amide unit of an N-methyl N-acyl­hydrazone derivative suggested that the amino spacer does not participate as a hydrogen-bond donor in the stabilization of the conformational isomers in solution (Lacerda et al., 2012). Prompted by the biological and structural importance of Schiff bases, as part of our structural studies (Gowda et al., 2000; Rodrigues et al., 2011; Jyothi & Gowda, 2004; Usha & Gowda, 2006; Purandara et al., 2015), we report herein on the synthesis, characterization and crystal structure of the title compound, (I), a new N-acyl­hydrazone derivative.

S2. Structural commentary

The title compound crystallizes as a monohydrate (Fig. 1). The conformation of the N—H bond in the amide part is anti with respect to both the C═ O bonds in the molecule, while the N—H bond in the hydrazone part is syn to both the C═O(hydrazone) and the C—H (imine) bonds. The C9—O2 bond length of 1.2251 (19) Å indicates that the molecule exists in the keto form in the solid state, and the C10—N3 bond length of 1.271 (2) Å confirms its significant double-bond character. The C9—N2 and N2—N3 bond distances of 1.351 (2) and 1.3771 (18) Å, respectively, indicate a significant delocalization of the π-electron density over the hydrazone portion of the molecule. Variations in the C—N bond lengths of 1.330 (2), 1.442 (2) and 1.351 (2) Å for C7—N1, C8—N1 and C9—N2, respectively, characterize mobility of the bridge and the integral flexibility of the –C(═O)–NH–CH₂C(═O)–NH—N=CH– group connecting the two benzene rings. The molecule is twisted at atom C8, the C7—N1—C8—C9 torsion angle being 79.8 (2)°. The hydrazone part of the molecule is almost planar, with C9—N2—N3—C10 and N2—N3—C10—C11 torsion angles of -177.07 (15) and 179.38 (14)°, respectively. Further, the dihedral angle between the almost planar hydrazone segment (O2/N2/N3/C8–C11; maximum deviation of 0.029 (1) Å for atom N2) and the attached benzene ring (C11–C16) is 8.17 (6)°. The two benzene rings (C1–C6 and C11–C16) are orthogonal to each other, making a dihedral angle of 89.69 (9)°. The planar amide segment (O1/N1/C1/C7/C8; r.m.s. deviation = 0.009 Å) is inclined to the attached toluene ring (C1–C6) by 8.06 (9) Å.

S3. Supra­molecular features

In the crystal of (I), the amide carbonyl O-atom, O1, shows bifurcated hydrogen bonding (Table 1 and Fig. 2); one with the hydrazide hydrogen atom and the other with one of the hydrogen atoms of the water molecule (O3). The two hydrogen atoms of the water molecule are involved in hydrogen bonding with the O atoms of the amide carbonyl (O3—H31···O1) and glycine carbonyl (O3—H32···O2) groups of two different molecules of the title compound. The O atom is also involved in hydrogen bonding with the H atom of the carbonyl­amide group of a third symmetry-related molecule (N1—H1N···O3). A pair of N2—H2N···O1 inter­molecular hydrogen bonds link the molecules, forming inversion dimers, with an R₂²(14) ring motif. The dimers are further linked via hydrogen bonds involving the water molecule generating R₄⁴(14) and R₄⁴(18) ring motifs. Further, the N2—H2N···O1 and N1—H1N···O3 hydrogen bonds between the molecules of the main compound and water molecules translate into C₂²(6) chains along the a-axis direction (Table 1 and Fig. 2) The chains are linked by a C—H···O inter­action, forming sheets parallel to (010). Within the sheets there are C—H···π, and parallel slipped π–π stacking inter­actions [Cg2···Cg2ⁱ = 3.6458 (12) Å; inter-planar distance = 3.4135 (8) Å, slippage = 1.281 Å; Cg2 is the centroid of ring C11–C16; symmetry code: (i) -x + 1, -y + 1, -z + 1] involving inversion-related chloro­benzene rings; see Fig. 3.

S4. Database survey

A search of the Cambridge Structural Database (Version 5.36, May 2015; Groom & Allen, 2014) for the fragment –NH–CH₂–C(═O)–NH–N═CH–, yielded only one hit, namely N-(2-hy­droxy-1-naphthyl­methyl­ene)-N'-(N-phenyl­glycyl)hydrazine (MEMTOO; Gudasi et al., 2006). A comparison of the structural details of the title compound, (I), with those of the recently published sulfonyl derivative, (E)-N-{2-[2-(3-chloro­benzyl­idene)hydrazinyl]-2-oxo­ethyl}-4-methyl­benzene­sulfonamide monohydrate (II) (Purandara et al., 2015), reveals the trans orientation of the amide group (C1–C7(═O1)N1) and hydrazone segment (N2–N3═C10–C11) with respect to the glycinyl C8—C9 bond in (I), as is evident from the N1—C8—C9—N2 torsion angle of 173.58 (15)°, in contrast to the cis orientation of the sulfonamide and hydrazone segments, with respect to the glycinyl C—C bond, observed in compound (II). In the structure of (I), the benzene ring (C1–C6) is almost coplanar with the amide group [dihedral angle = 8.21 (13)°]. This is in contrast to the L-shaped conformation (bent at the S atom) of the sulfonamide group with respect to the benzene ring in compound (II). The amide carbonyl O atom forms stronger O—H···O hydrogen bonds with the water H atoms than the sulfonyl O atom as observed in compound (II), indicating the stronger electron-withdrawing character of the amide group compared to the sulfonamide group.

S5. Synthesis and crystallization

Tri­ethyl­amine (0.03 mol) and 4-methyl­benzoyl chloride (0.01 mol) were added to a stirred suspension of glycine ethyl­ester hydro­chloride (0.01 mol) in di­chloro­methane (50 ml) in an ice bath. The reaction mixture was stirred at room temperature for 20 h. After completion of the reaction, 2N hydro­chloric acid (80 ml) was added slowly. The organic phase was separated and washed with water (30 ml), dried with anhydrous Na₂SO₄ and evaporated to yield the corresponding ester, N-(4-methyl­benzoyl)­glycine ethyl ester (L1). L1 (0.01 mol) was added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol. The mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to give N-(4-methyl­benzoyl)-glycinyl hydrazide (L2). 2-Chloro­benzaldehyde (0.01 mol) and two drops of glacial acetic acid were added to L2 (0.01 mol) in anhydrous methanol (30 ml). The reaction mixture was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (479–480 K). Prism-like colourless single crystals of the title compound were grown from a solution in DMF by slow evaporation of the solvent.

The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3323.3, 3203.8, 1685.8, 1620.2 and 1566.2 cm^-1 for the stretching bands of N—H (amide I), N—H (amide II), C═O(hydrazone), C═O(amide) and C═N, respectively. The characteristic ¹H and ¹³C NMR spectra of the title compound are as follows: ¹H NMR (400 MHz, DMSO-d6, δ p.p.m.): 2.36 (s, 3H), 4.01, 4.45 (2d, 2H, J = 5.8 Hz), 7.25 (d, 2H, Ar—H, J = 8.0 Hz), 7.33–7.40 (m, 2H, Ar—H), 7.42–7.45 (m, 1H, Ar—H), 7.81 (d, 2H, Ar—H), 7.97–7.99 (m, 1H, Ar—H), 8.39, 8.63 (2s, 1H), 8.54, 8.76 (2t, 1H, J = 5.7 Hz), 11.65, 11.73 (2s, 1H). ¹³C NMR (400 MHz, DMSO-d6, δ p.p.m.): 20.97, 40.74, 42.04, 126.60, 126.83, 127.28, 128.64, 129.66, 130.85, 131.35, 133.10, 139.45, 141.06, 142.70, 165.98, 166.54, 170.48.

S6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The water H atoms and the NH H atoms were located in a difference Fourier map and refined with distances restraints: O—H = 0.85 (2), N—H = 0.86 (2) Å with U_iso(H) = 1.5U_eq(O) and 1.2U_eq(N). The C-bound H atoms were positioned with idealized geometry and refined as riding atoms: C—H = 0.93–0.97 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Related literature

For related literature, see: Groom & Allen (2014); Gudasi et al. (2006); Jyothi & Gowda (2004); Lacerda et al. (2012); Osorio et al. (2012); Palla et al. (1986); Rodrigues et al. (2011); Usha & Gowda (2006).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Hydrogen-bonding pattern in the title compound (see Table 1 for details). [Symmetry codes: (a) -x + 1, -y + 1, -z; (d) x + 1, y, z; (e) x, y, z + 1.]
	Fig. 3. A view along the a axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines and C—H···π interactions are represented as red arrows (see Table 1 for further details).

(E)-N-{2-[2-(2-Chlorobenzylidene)hydrazin-1-yl]-2-oxoethyl}-4-methylbenzamide monohydrate

Crystal data

C17H16ClN3O2·H2O	Z = 2
Mr = 347.79	F(000) = 364
Triclinic, P1	Dx = 1.379 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9729 (7) Å	Cell parameters from 3287 reflections
b = 10.642 (1) Å	θ = 3.1–27.7°
c = 11.879 (1) Å	µ = 0.25 mm^−1
α = 95.049 (8)°	T = 293 K
β = 100.324 (9)°	Prism, colourless
γ = 102.870 (9)°	0.50 × 0.40 × 0.32 mm
V = 837.88 (14) Å^3

Data collection

Oxford Diffraction Xcalibur single crystal X-ray diffractometer with a Sapphire CCD detector	3393 independent reflections
Radiation source: fine-focus sealed tube	2829 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.009
Rotation method data acquisition using ω scans	θmax = 26.4°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −7→8
Tmin = 0.886, Tmax = 0.925	k = −12→13
5538 measured reflections	l = −14→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0396P)^2 + 0.4048P] where P = (Fo^2 + 2Fc^2)/3
3393 reflections	(Δ/σ)max < 0.001
230 parameters	Δρmax = 0.24 e Å^−3
4 restraints	Δρmin = −0.33 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.60321 (11)	0.19118 (5)	0.47068 (5)	0.0724 (2)
O1	0.62994 (17)	0.78208 (12)	−0.04768 (11)	0.0451 (3)
O2	0.7257 (2)	0.49520 (12)	−0.03656 (10)	0.0499 (3)
N1	0.9290 (2)	0.75016 (14)	0.03466 (12)	0.0417 (3)
H1N	1.054 (2)	0.766 (2)	0.0404 (17)	0.050*
N2	0.6958 (2)	0.45136 (14)	0.14178 (11)	0.0395 (3)
H2N	0.617 (3)	0.3748 (16)	0.1142 (16)	0.047*
N3	0.7330 (2)	0.49621 (14)	0.25783 (11)	0.0365 (3)
C1	0.9132 (2)	0.87432 (15)	−0.12558 (13)	0.0340 (3)
C2	0.8034 (3)	0.93929 (18)	−0.19759 (16)	0.0470 (4)
H2	0.6703	0.9352	−0.1934	0.056*
C3	0.8883 (3)	1.0105 (2)	−0.27602 (17)	0.0543 (5)
H3	0.8112	1.0537	−0.3235	0.065*
C4	1.0838 (3)	1.01864 (17)	−0.28502 (15)	0.0471 (4)
C5	1.1929 (3)	0.9537 (2)	−0.21334 (17)	0.0551 (5)
H5	1.3259	0.9581	−0.2179	0.066*
C6	1.1104 (3)	0.8822 (2)	−0.13474 (17)	0.0503 (5)
H6	1.1879	0.8390	−0.0876	0.060*
C7	0.8130 (2)	0.79820 (15)	−0.04311 (13)	0.0349 (3)
C8	0.8517 (3)	0.67330 (17)	0.11810 (14)	0.0418 (4)
H8A	0.7536	0.7113	0.1479	0.050*
H8B	0.9608	0.6755	0.1822	0.050*
C9	0.7542 (2)	0.53317 (16)	0.06684 (13)	0.0365 (4)
C10	0.6807 (2)	0.41135 (17)	0.32262 (14)	0.0383 (4)
H10	0.6205	0.3256	0.2906	0.046*
C11	0.7154 (2)	0.44844 (17)	0.44785 (13)	0.0365 (4)
C12	0.6834 (3)	0.35608 (18)	0.52341 (15)	0.0426 (4)
C13	0.7134 (3)	0.3916 (2)	0.64139 (15)	0.0517 (5)
H13	0.6894	0.3284	0.6899	0.062*
C14	0.7787 (3)	0.5207 (2)	0.68642 (16)	0.0558 (5)
H14	0.7984	0.5451	0.7656	0.067*
C15	0.8151 (3)	0.6143 (2)	0.61429 (16)	0.0539 (5)
H15	0.8613	0.7016	0.6448	0.065*
C16	0.7828 (3)	0.57766 (19)	0.49659 (15)	0.0453 (4)
H16	0.8069	0.6415	0.4487	0.054*
C17	1.1791 (4)	1.0976 (2)	−0.36898 (19)	0.0688 (6)
H17A	1.0858	1.1420	−0.4073	0.103*
H17B	1.2140	1.0409	−0.4252	0.103*
H17C	1.2981	1.1602	−0.3279	0.103*
O3	0.3605 (2)	0.76894 (15)	0.11275 (13)	0.0555 (4)
H31	0.452 (3)	0.799 (3)	0.078 (2)	0.083*
H32	0.340 (4)	0.6869 (17)	0.094 (2)	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1083 (5)	0.0530 (3)	0.0572 (3)	0.0101 (3)	0.0233 (3)	0.0258 (2)
O1	0.0388 (6)	0.0496 (7)	0.0445 (7)	0.0007 (5)	0.0129 (5)	0.0100 (5)
O2	0.0698 (9)	0.0503 (7)	0.0277 (6)	0.0064 (6)	0.0134 (6)	0.0093 (5)
N1	0.0383 (7)	0.0470 (8)	0.0364 (7)	−0.0009 (6)	0.0082 (6)	0.0159 (6)
N2	0.0474 (8)	0.0396 (8)	0.0278 (7)	0.0010 (6)	0.0081 (6)	0.0094 (6)
N3	0.0372 (7)	0.0458 (8)	0.0270 (6)	0.0077 (6)	0.0077 (5)	0.0115 (6)
C1	0.0395 (8)	0.0314 (8)	0.0285 (7)	0.0016 (6)	0.0088 (6)	0.0038 (6)
C2	0.0442 (10)	0.0510 (10)	0.0485 (10)	0.0116 (8)	0.0115 (8)	0.0165 (8)
C3	0.0641 (12)	0.0526 (11)	0.0495 (11)	0.0152 (9)	0.0112 (9)	0.0241 (9)
C4	0.0656 (12)	0.0367 (9)	0.0349 (9)	−0.0020 (8)	0.0169 (8)	0.0061 (7)
C5	0.0463 (10)	0.0709 (13)	0.0527 (11)	0.0093 (9)	0.0227 (9)	0.0204 (10)
C6	0.0454 (10)	0.0651 (12)	0.0476 (10)	0.0167 (9)	0.0155 (8)	0.0250 (9)
C7	0.0384 (8)	0.0322 (8)	0.0303 (8)	−0.0005 (6)	0.0090 (6)	0.0028 (6)
C8	0.0467 (9)	0.0454 (9)	0.0290 (8)	0.0003 (7)	0.0072 (7)	0.0117 (7)
C9	0.0379 (8)	0.0433 (9)	0.0288 (8)	0.0075 (7)	0.0077 (6)	0.0115 (7)
C10	0.0424 (9)	0.0427 (9)	0.0322 (8)	0.0093 (7)	0.0112 (7)	0.0126 (7)
C11	0.0328 (8)	0.0508 (10)	0.0308 (8)	0.0137 (7)	0.0102 (6)	0.0153 (7)
C12	0.0396 (9)	0.0558 (10)	0.0377 (9)	0.0141 (8)	0.0123 (7)	0.0196 (8)
C13	0.0470 (10)	0.0817 (15)	0.0340 (9)	0.0208 (10)	0.0120 (8)	0.0276 (9)
C14	0.0490 (11)	0.0920 (16)	0.0288 (9)	0.0226 (10)	0.0071 (8)	0.0091 (9)
C15	0.0540 (11)	0.0652 (13)	0.0408 (10)	0.0157 (9)	0.0067 (8)	0.0015 (9)
C16	0.0478 (10)	0.0527 (11)	0.0382 (9)	0.0135 (8)	0.0112 (7)	0.0140 (8)
C17	0.0966 (17)	0.0565 (12)	0.0513 (12)	−0.0029 (12)	0.0318 (12)	0.0176 (10)
O3	0.0576 (8)	0.0586 (8)	0.0554 (8)	0.0145 (7)	0.0223 (7)	0.0109 (7)

Geometric parameters (Å, º)

Cl1—C12	1.740 (2)	C6—H6	0.9300
O1—C7	1.240 (2)	C8—C9	1.516 (2)
O2—C9	1.2251 (19)	C8—H8A	0.9700
N1—C7	1.330 (2)	C8—H8B	0.9700
N1—C8	1.442 (2)	C10—C11	1.467 (2)
N1—H1N	0.842 (15)	C10—H10	0.9300
N2—C9	1.351 (2)	C11—C16	1.386 (3)
N2—N3	1.3771 (18)	C11—C12	1.397 (2)
N2—H2N	0.873 (15)	C12—C13	1.385 (3)
N3—C10	1.271 (2)	C13—C14	1.373 (3)
C1—C2	1.379 (2)	C13—H13	0.9300
C1—C6	1.383 (2)	C14—C15	1.381 (3)
C1—C7	1.496 (2)	C14—H14	0.9300
C2—C3	1.384 (3)	C15—C16	1.382 (3)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.371 (3)	C16—H16	0.9300
C3—H3	0.9300	C17—H17A	0.9600
C4—C5	1.373 (3)	C17—H17B	0.9600
C4—C17	1.510 (2)	C17—H17C	0.9600
C5—C6	1.380 (2)	O3—H31	0.840 (17)
C5—H5	0.9300	O3—H32	0.856 (17)
C7—N1—C8	122.85 (15)	H8A—C8—H8B	107.9
C7—N1—H1N	121.7 (14)	O2—C9—N2	121.16 (16)
C8—N1—H1N	115.4 (14)	O2—C9—C8	122.74 (14)
C9—N2—N3	119.90 (14)	N2—C9—C8	116.08 (14)
C9—N2—H2N	118.6 (13)	N3—C10—C11	120.13 (16)
N3—N2—H2N	120.7 (13)	N3—C10—H10	119.9
C10—N3—N2	115.65 (14)	C11—C10—H10	119.9
C2—C1—C6	117.83 (15)	C16—C11—C12	116.92 (16)
C2—C1—C7	118.58 (15)	C16—C11—C10	121.14 (15)
C6—C1—C7	123.59 (15)	C12—C11—C10	121.94 (16)
C1—C2—C3	121.00 (17)	C13—C12—C11	121.76 (18)
C1—C2—H2	119.5	C13—C12—Cl1	117.92 (14)
C3—C2—H2	119.5	C11—C12—Cl1	120.32 (14)
C4—C3—C2	121.22 (18)	C14—C13—C12	119.63 (17)
C4—C3—H3	119.4	C14—C13—H13	120.2
C2—C3—H3	119.4	C12—C13—H13	120.2
C3—C4—C5	117.71 (16)	C13—C14—C15	120.05 (17)
C3—C4—C17	121.75 (19)	C13—C14—H14	120.0
C5—C4—C17	120.53 (19)	C15—C14—H14	120.0
C4—C5—C6	121.76 (18)	C14—C15—C16	119.8 (2)
C4—C5—H5	119.1	C14—C15—H15	120.1
C6—C5—H5	119.1	C16—C15—H15	120.1
C5—C6—C1	120.49 (17)	C15—C16—C11	121.87 (17)
C5—C6—H6	119.8	C15—C16—H16	119.1
C1—C6—H6	119.8	C11—C16—H16	119.1
O1—C7—N1	122.19 (14)	C4—C17—H17A	109.5
O1—C7—C1	120.78 (15)	C4—C17—H17B	109.5
N1—C7—C1	117.03 (14)	H17A—C17—H17B	109.5
N1—C8—C9	112.26 (14)	C4—C17—H17C	109.5
N1—C8—H8A	109.2	H17A—C17—H17C	109.5
C9—C8—H8A	109.2	H17B—C17—H17C	109.5
N1—C8—H8B	109.2	H31—O3—H32	102 (3)
C9—C8—H8B	109.2
C9—N2—N3—C10	−177.07 (15)	N3—N2—C9—O2	178.83 (15)
C6—C1—C2—C3	−0.3 (3)	N3—N2—C9—C8	−2.4 (2)
C7—C1—C2—C3	−179.62 (17)	N1—C8—C9—O2	−7.6 (2)
C1—C2—C3—C4	0.2 (3)	N1—C8—C9—N2	173.58 (15)
C2—C3—C4—C5	−0.1 (3)	N2—N3—C10—C11	179.38 (14)
C2—C3—C4—C17	−179.09 (19)	N3—C10—C11—C16	7.7 (2)
C3—C4—C5—C6	0.1 (3)	N3—C10—C11—C12	−171.98 (16)
C17—C4—C5—C6	179.14 (19)	C16—C11—C12—C13	1.3 (2)
C4—C5—C6—C1	−0.3 (3)	C10—C11—C12—C13	−179.00 (16)
C2—C1—C6—C5	0.3 (3)	C16—C11—C12—Cl1	−178.83 (13)
C7—C1—C6—C5	179.62 (17)	C10—C11—C12—Cl1	0.9 (2)
C8—N1—C7—O1	1.4 (3)	C11—C12—C13—C14	−0.8 (3)
C8—N1—C7—C1	−179.01 (15)	Cl1—C12—C13—C14	179.30 (15)
C2—C1—C7—O1	7.7 (2)	C12—C13—C14—C15	−0.3 (3)
C6—C1—C7—O1	−171.59 (17)	C13—C14—C15—C16	0.9 (3)
C2—C1—C7—N1	−171.90 (16)	C14—C15—C16—C11	−0.4 (3)
C6—C1—C7—N1	8.8 (2)	C12—C11—C16—C15	−0.7 (3)
C7—N1—C8—C9	79.8 (2)	C10—C11—C16—C15	179.63 (17)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the toluene ring C1–C6.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···O1	0.84 (2)	2.13 (2)	2.897 (2)	152 (3)
O3—H32···O2^i	0.86 (2)	1.92 (2)	2.772 (2)	174 (3)
N1—H1N···O3^ii	0.84 (2)	2.15 (2)	2.941 (2)	158 (2)
N2—H2N···O1^i	0.87 (2)	2.09 (2)	2.944 (2)	165 (2)
C14—H14···O2^iii	0.93	2.57	3.404 (2)	150
C15—H15···Cg1^iii	0.93	2.89	3.793 (2)	165

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) x, y, z+1.